Dipropylacetylanilides

ABSTRACT

DIPROPYLACETYLAMILIDE AND THE NUCLEAR SUBSTITUTED HYDROXY, ALKOXY, HALO, NITRO, HALOMETHYL, AMINO, AMIDO OR ALKYL DEDIVATIVES ARE DESCRIBED WHICH ARE USEFUL AS INTERMEDIATES IN ORGANIC SYNTHESIS AMD AS FOOD PRESERVATIVES.

United States Patent Ofice 3,555,091 DIPROPYLACETYLANILIDES Jean-Louis Alain Benoit-Guyod and Andr Louis Boucherle Grenoble, France, assiguors to Laboratoires J. Bertluer, Grenoble, France, a French company 3,555,091 Patented Jan. 12, 1971 These products are useful as intermediates in the syn-. thesis of organic compounds, or as preservative agents in the food industry. They are also useful as analgesic, antipyretic and antiinilammatory agents which use is the subject of a U.S. patent application filed simultaneously here- No l )rawi ng. Filed ct. 6, 19 7; Set. N0. 673,267 with,

c l'l' ya l gi g i r 1967, The present invention aims at the following products II'ILQL i 103/30 more particularly: 4 hydroxy dipropylacetylanilide in Us. (:1. 260,562 I s 6 Claims Whlch 3 l R5=H and R1=OH;

' 1O propylacetylanlhde 1n which R R R and R =H nd R =OC H 4-methoxy dipropylacetylanilide in which R THE DISCLOSURE R R and lQ Pl and R =OCH 4-trifluorornethyl di- 7, Dip ropyla cetylanil ide d the nuclear substituted propylacetanrhde 1n which R R R and R =H and droxy, alkoxy, halo, nitro, halomethyl, amino, amido or 1= 3; 4-acetvlamid0 dlpropylacetanilide in which 2 alkyl dedivatives are described which are useful as inter- 5 4 and R H and R '--NH-C y mediates in organic synthesisand as food preservatives. dlpropylacetylamhde in which 2, 3. 4 and 5= and R =CH 4-chloro dipropylacetylanilide in which R R w r R and R =H and R =Cl; 3 -trifluoromethyl dipropyl- 31 9E y g fql t w chemlcal acetanilide in which R R R and R =H and R =CF Td PO 10 t fl 1 e y rv 0 p p fy 3,5-bistrifluoromethyl dipropylacetanilide in which R R 1 1 e correspon mg ot e o ,owlng general formula. and R5=H and R2 and RazcFa; 3 methoxy dipropyl acetylanilide in which R R R and R =H and R 4 OCH Z-trifluoromethyl dipropylacetanilide in which R Rh 5 3 R R and R =H and R =CF Z-methoxy dipropyl- R 6 2 acetylanilide in which R R R and R =H and R \1/ C3117 OCH 2,4-dichloro dipropylacetanilide in which R R and R =H and R and R =Cl; 3,4-dichloro dipropyl- 'T Q acetanilide in which R R and R :H and R and R =Cl; C(iHT 3,4,6-trichloro dipropylacetanilide in which R and R =H 1n Wl'llCh R R R R R are together or separately: a and R R and R =Cl; 2,4-dimethyl dipropylacetylanilide hydrogen atom; a hydroxyl group, plain or substituted by, in which R R and R =H and R and R =CH 3,4- m particular, a methyl group, an ethyl group, a butyl dimethyl dipropylacetylanilide in which R R and R =H group, a propyl group, or otherwise; an atom of halogen, and R and R =CH 2-methoxy-3-nitro dipropylacetylanor an N0 group; a halomethyl group such as C01 or ilide in which R R and R =H and R =NO and R CBr or CE; or CI an amine group or one of the corre- OCH 5 trifluoromethyl 2 chloro dipropylacetanilide sponding amides; or a methyl, ethyl, butyl, propyl or other in which R R and R =H and R =Cl and R =CF group. The physico-chemical chemical characteristics of these The previously described organic or halogen radical can particular products are summarized in the following table.

Percentage of the principal elements Melting point F. Yield, 0% H% N% Coucenafter R% of tration recrystalthe Caleu- Caleu- Calcu- Name of product alcohol Appearance lization reaction lated Found lated Found lated Found 4-hydroxy dipropylacetylanilide 96 Beige pink 104 64 71. 95 71. O3 8. 99 8.86 5. 95 6. 21

crystgtlline W 81- 4-ethoxy dipropylacetylauilide wl ii ie tarystalliue 153 92 72. 96 72.88 9.57 9.65 5.32 5. 63 4-meth0xy dipropylacetylanilide 164 50 72.25 72.04 9. 3O 9. 26 5. 62 5. 67 4-trifluoro methyldipropylacetanilide. 157 74 62. 72 62. 66 7. 02 7. 03 4. 88 4. 97 4-acetylamido dipropylaoetanilide 250 71 68.39 69. 35 9.08 8.86 10.55 10.27 4-methy1 dipropylacetylanilide 154 81 77. 21 76. 88 9. 93 9. 84 6. 6. 03 4-chloro dipropylacetylanilide 175 87 66. 26 66. 25 7. 94 7. 82 5. 52 5. 54 3-trifluoromethyldipropylacetanilide 64 62.72 62.56 7.02 6.97 4.88 4. 97 3,5-ditrifluoromethyldipropylacetani e. 153 89 54.08 54.36 5. 39 5.42 3.94 3.86 B-methoxy dipropylacetylanilide 110 81 72. 25 72. 12 9. 30 9. 25 5. 62 5. 56 2-trifluoro methyldipropylacetanilide. 100 76 62. 72 62. 60 7. 02 7. 12 4.88 4. 98 2-methoxy dipropylacetylanilide 143 80 72. 25 72. 16 9. 30 9. 20 5. 62 5. 72 2,4-dichloro dipropylacetauilide 103. 5 62 58. 34 58.01 6. 64 6. 62 4. 86 4. 84 3,4-dichloro dipropylacetanilide 124 81 58. 34 58. 10 6. 64 6. 52 4. 85 4. 97 3,4,6-n-ieh16r6 dipropylacetanilide 124.5 85 52.11 52. 29 5.62 5.50 4. 34 4.53 2,4-dimethyl dipropylacetylanilide- 140 98 77.68 77. 27 10. 19 10.16 5. 66 5. 59 3,4-dimethyl dipropylacetylanilide. 109 49 77.68 77. 47 10. 19 9. 97 5. 66 5. 60 2-methoxy-3-nitro dipropylacetylanilide. 122 17 61.21 60. 7. 53 7. 56 9. 52 9.70 5-trifluour-methyl-2-chloro dipropylacet- 77 49 55. 00 55. 91 5. 95 6. l2 4. 35 4. 45

anilide.

1 Used for recrystallization for preparation, percentage. be substituted as mono or plural substituents in ortho, The following examples are presented in order to dismeta, or para positions, or a combination of the two, in close the invention more fully. It should be understood, the dipropylacetylanilide, corresponding to the following however, that they are not intended to limit the invenformula: I 65 tion in any way.

EXAMPLE I Preparation of dipropylacetyl hydroxy-4-anilide O H 4.89 gm. of dipropylacetyl chloride (30 millimoles) are a 7 70 heated at reflux for one hour with 6.54 gm. of para aminophenol (60 rnillimoles) in solution in ml. of 0,117 anhydrous dioxane. The reaction mixture is evaporated and the residue is dissolved in 20 ml. of ethyl alcohol at 96. The hot solution is filtered, the filtrate is cooled to and crushed ice is added very slowly until precipitation is completed. This operation is repeated several times.

EXAMPLE II Preparation of the other anilides All the other anilides according to the invention can be obtained by the action of 30 rnillimoles of dipropylacetyl chloride on 60 millimoles of the corresponding substituted anilide, only varying the concentration of the ethyl alcohol for recrystallization (see the column on the left in the above table).

The preparation of dipropylacetyl-chloro-Z-trifluoromethyl-S-anilide will be given in detail only by way of example.

EXAMPLE III 4.89 gm. of dipropylacetyl chloride (30 millimoles) are placed in contact with 11.76 gm. of chloro-2-trifiuoromethyl-S-anilin'e (60 millimoles) at ambient temperature over a period of minutes. A precipitate is formed which is separated. The filtrate is washed by agitation with water in a separatory funnel until the aqueous phase no longer gives any turbidity with silver nitrate in nitric medium. The aromatic phase is then dried and evaporated. The residue is purified by precipitation by water from its alcoholic solution.

Others may practice the invention in any of the numerous ways which will be suggested by this disclosure to one skilled in the art by employing one or more of the novel features disclosed or equivalents thereof. All such practice of the invention is considered to be a part hereof provided it falls within the scope of the appended claims.

4 We claim: 1. A compound of the formula @NHCOCH(C:H7)2 RI References Cited UNITED STATES PATENTS 3,418,345 12/1968 Baker 260562 3,407,056 10/ 1968 Schwartz 260562 3,281,467 10/1966 Wilson et al. 260562 OTHER REFERENCES Benoit-Guyod et al., Bull. Soc. Chim. Fr. (1965), pp. 1660-1661.

HENRY R. JILES, Primary Examiner H. I. MONTZ, Assistant Examiner US. Cl. X.R. 424324 

